Process for preparation of high resilience polyether urethane foam

ABSTRACT

A process for producing high resilience polyether urethane foam using a cyanoalkyl modified siloxane fluid; the foams derived therefrom; a solvent-solution of said siloxane; and cyanoalkyl modified siloxane fluids per se.

Prokai 1 1 Sept. 16, 1975 [54] PROCESS FOR PREPARATION OF HIGH 3,185,7195/1965 Prober 260/465 R RESHJENCE POLYETTIER URE'IHANE 3,531,508 9/[970Goldman 260/465 E FOAM V 3,706,681 l2/l972 Bachura 1 4 260/25 AH3,74l,9l7 6/l973 Morehouse. .1 260/25 AP [75] Inventor: Bela Prokai,Mahopac, NY. 3,790,612 2/1974 Raleigh 260/25 AH 3,839,384 lO/l974Morehouse. 260/25 AH Assigfleei Union Carbide Corporation, New 3,846,46211/1974 Prokai 260/215 AH York, NY.

[22] Filed: June 1974 Primary ExaminerMelvyn l. Marquis [2|] App] No;475,967 Assistant ExaminerC. Warren lvy Attorney, Agent, or Firm-R. .l.Finnegan Related US. Application Data [63] Continuation-impart 0f Ser,No. 325,327, Jan. 22,

1973, abandoned. 57 ABSTRACT [52] US. Cl...... 25 AH; 260/4482 N;260/4488 R A process for producing high resilience polyether ure- [5 l]Int. Cl. C08G 18/14; CO8G 18/48 thane foam using a cyanoalkyl modifiedsiloxane fluid; [58] Field of Search. 260/25 AH, 448.2 N, 448.8 R thefoams derived therefrom; a solvent-solution of said siloxane; andcyanoalkyl modified siloxane fluids per [56] References Cited se.

UNITED STATES PATENTS 28 Claims, No Drawings 3,185,663 5/1965 Prober H260/465 R PROCESS FOR PREPARATION OF HIGH RESILIENCE POLYETHER URETHANEFOAM This application is a continuation in part of US. Ap-

plication Ser. No. 325,327 filed Jan. 22, 1973, now abandoned.

BACKGROUND OF THE INVENTION This invention relates to high resiliencepolyurethane foams and more particularly to the use of certainorganosilicon polymers in the production of such foams.

Basically such high resilience foams are produced by the reaction ofhighly primary hydroxylcapped, high molecular weight polyols withorganic isocyanates and water. High resilience polyurethane foams aredistinguishable in part from conventional hot cure polyurethane foams bythe use of such polyols and the fact that high resilience polyurethanefoams require little or no over curing and thus are often referred to ascold cure foams. Such foams are extremely desirable for cushioningapplications because of their excellent physical properties, e.g. veryhigh foam resilience, low flammability, open-celled structure, low flexfatigue (long life) and high SAC factors (load bearing properties).

Because of the high reactivity of high resilience foam ingredients andtheir rapid buildup of gel strength, sometimes the foam can be obtainedwithout a cell stabilizer. however such foams typically have veryirregular cell structure as particularly evidenced by surface voids andthe discovery of a proper agent to help control cell structure hasremained a major problem in the art.

Attempts to solve this problem with surfactants gen erally employed inthe stabilization of hot cure polyurethane foam have not provensatisfactory because such surfactants tend to overstabilize, causingextremely tight, shrinkaging foam. Nor is the problem corrected byreducing the concentrations of such surfactants, since at concentrationsrequired to eliminate shrinkage, the cells are no longer stabilizedsatisfactorily and the foam structure becomes irregular, coarse andcontains surface voids.

The use oflow viscosity dimethylsilicone oils alone as stabilizers forhigh resilience foams also has various disadvantages. For example, atlow concentrations they create metering and pumping problems in theprocessing of the foam, while at higher concentrations these oilsadversely affect the physical properties of the foams. Solvents for suchdimcthylsiloxane oils that are nonreactive with the foam ingredientse.g. alkanes, hexamethyldisiloxane, and the like, can adversely affectthe foams physical properties in proportion to their concentration andgenerally create flammability hazards. Furthermore isocyanate reactivediluents, such as polyether triols and the like which do notsignificantly change the foams properties, inasmuch as they react intothe system and become part of the foam structure, are not satisfactorysolvents for dimethylsilicone oils, since not enough oil can bedissolved to provide foam stabilization at practical solutionconcentrations. High resilience foams are also adversely affected bydimethylsilicones having more than about l dimethylsiloxy units persiloxane. For example only five or ten weight per cent of such speciesin a dimethyl silicone oil can appreciably degrade the foams physicalproperties and even cause foam shrinkage.

Moreover, while particularly unique high resilience polyether urethanefoam can be prepared employing certain siloxane-oxyalkylene blockcopolymers as disclosed in US. Pat. Application Ser. No. 84,181 filedOct. 26, 1970, now US. Pat. No. 3,74l,9l7 or certain aralkyl modifiedsiloxane polymers as disclosed in US. Pat. Application Ser. No. 305,7l3filed Nov. 13, 1972, now US. Pat. No. 3,839,384 said disclosures do notteach the use of the novel organosilicon polymers employed in thisinvention.

SUMMARY OF THE INVENTION It has been discovered that flexible highresilience polyether urethane foam can be prepared according to theinstant invention which involves employing certain novel siloxanepolymer fluids as more fully defined below.

The siloxane polymer fluids employed in this inven tion have been foundto control the cell uniformity of high resilience polyether urethanefoam without obtaining tight foam and without introducing foam shrinkageor causing any severe adverse effects to the foams physical properties,e.g. the foams resilience and its resistance towards flammability.Moreover voids in the foam are eliminated by the instant invention andthe cell structure of the foam is also much more uniform and finer thanwhere no stabilizing agent is employed. This discovery is surprisingsince as outlined above not all surfactants are so suitable for use inthe production of high resilience foams. Indeed even siloxane polymerfluids of the same type employed herein, but outside the scope of theinstant invention, were found to cause shrinkage of the foam or not toeliminate the voids of the foam.

Therefore it is an object of this invention to provide a process forproducing high resilience polyether urethane foam. it is further anobject of this invention to provide novel organosilicon fluids for usein said process. It is still another object of this invention to providenovel compositions of said fluids for use in said process. It is alsoanother object of this invention to provide high resilience polyetherurethane foams produced by said process. Other objects and advantages ofthis invention will become readily apparent from the followingdescription and appended claims.

More particularly this invention is directed. in part, to a process forpreparing high resilience polyether urethane foam, said processcomprising foaming and reacting a reaction mixture comprising:

I. an organic polyol selected from the group consisting of (A) apolyether triol containing at least 40 mole per cent primary hydroxylgroups and having a molecular weight from about 2,000 to about 8,000 and(B) a mixture of said polyether triol and other polyethers having anaverage of at least two hydroxyl groups, said polyether triol of saidmixture amounting to at least 40 weight per cent of the total polyolcontent;

ll. an organic polyisocyanate, said organic polyol and saidpolyisocyanate being present in the mixture in a major amount and in therelative amount required to produce the urethane;

III. a blowing agent in a minor amount sufficient to foam the reactionmixture;

IV. a catalytic amount of a catalyst for the production of the urethanefrom the organic polyol and polyisocyanate; and

V. a minor amount of a cyanoalkyl modified siloxane fluid having theaverage formula (X )z Il z i( 2 ).ri X =H wherein x has a value of l to6 inclusive; v has a value of 0 to 6 inclusive; z has a value of 0 to linclusive; R is a lower alkyl or pbenyl radical; and X is a cyanoalkylradical of the formula wherein n has a value of 0 or l and R is analkylene radical having from 2 to 4 carbon atoms; said siloxane fluidcontaining at least one of said cyanoalkyl radicals and having anaverage molecular weight in the range of about 400 to L500.

It is to be understood of course that the above process and the appendedclaims read on employing a single ingredient of the type specified orany of the various combinations of ingredient mixtures possible. Forexample. in addition to employing a single ingredient of the typesspecified, if desired, a mixture of triols. a mixture ofpolyisocyanates. a mixture of blowing agents. a mixture of catalystsand/or a mixture of siloxane fluids can be employed. Likewise thetriol-polyether starting mixture could consist of a single triol and amixture of polyethers, a mixture of triols and a single polyether or amixture of two or more triols and two or more polyethers.

DESCRIPTION OF THE PREFERRED EMBODIMENTS As indicated above thecyanoalkyl modified siloxane fluid compounds employed as the siloxanestabilizers for cell control in this invention are characterized ashaving an average molecular weight range. as contain ing dihydrocarbylsiloxy units (R SiO) and siloxy units containing a cyanoalkyl radical ltis of course to be understood that the individual internal siloxy unitscan be the same or different and can be arranged in any order. Subjectto the above qualifications. a more detailed description of thecyanoalkyl modified siloxane fluids is presented below.

Accordingly the siloxane surfactants useful in this invention containinternal dihydrocarbyl siloxy units. such as dimethylsiloxy.diethylsiloxy. dipropylsiloxy. methylethylsiloxy. methylphenylsiloxygroups. and the like. Examples of internal cyanoalkyl siloxy units thatcan be present in said siloxanes include, c.g. (betacyanoethoxy)methylsiloxy. (beta-cyanoethyl) methylsiloxy. (betacyanopropyl)methylsiloxy, (gammacyanopropyl) methylsiloxy. (gamma-cyanopropyloxy)xy-dimethylsiloxanes, trimethyl endblocked (delta cyanobutyl)methylsiloxy-dimethylsiloxanes, (gammacyanopropyloxy) dimethylend-blocked dimethylsiloxanes. (beta-cyanoethyl) dimethyl end-blockeddimethylsiloxanes, (beta-cyanopropyl) dimethyl endblockeddimethylsiloxanes, (gamma-cyanopropyl) dimethyl end-blockeddimethylsiloxanes, (deltacyanobutyl) dimethyl end-blockeddimethylsiloxanes. trimethyl end-blocked (beta-cyanoethyl) methylsiloxy-(gamma-cyanopropyl) methylsiloxy-dimethylsiloxanes.(gamma-cyanopropyloxy) dimethyl end-blocked- (gamma-cyanopropyloxy)methylsiloxydimethylsiloxanes. (beta-cyanoethyl) dimethyl cnd-blocked-(beta-cyanoethyl) methylsiloxydimethylsiloxanes, (beta-cyanopropyl)dimethyl endblocked-( beta-cyanopropyl) methylsiloxydimethylsiloxanes,(gamma-cyanopropyl) dimethyl end-blocked-( gamma-cyanopropyl)methylsiloxydimethylsiloxanes, and (delta-cyanobutyl) dimethylend-blocked-(deltacyanobutyl) methylsiloxydimethylsiloxanes, and thelike. Most preferably the cyanoalkyl radical is bonded directly to thesilicon atom through one of its carbon atoms, i.e., SiC instead ofthrough an oxygen atom. i.e., SiOC.

Furthermore it is considered that the above cyanoalkyl modified siloxanefluids having an average molecular weight in the range of about 400 toabout 1.500 employed as the cell stabilizers in this invention are novelcompounds per se. The preferred siloxane fluids are those having anaverage molecular weight range of about 400 to about 900. especially thetrimethyl endblocked (gamma-cyanopropyl) methylsiloxydimethylsiloxancs.

The siloxane fluids of this invention can be produced by any number ofconventional methods well known in the art. as shown e.g. by US. Pat.No. 3.221.040 and US. Pat. Application. Ser. No. 279.883 filed Aug. l l.[972, now U.S. Pat. No. 3,846,462. Preferably the siloxane fluidscontaining nonhydrolyzable cyanoalkyl radicals (Si-R'CN) are prepared byequilibration of corresponding siloxanes. cg. hexamethyldisiloxane.cyclic dimethyl siloxane and tetracyclic (gammacyanopropyl)methylsiloxane, using an acid or base catalyst. For instance they can beprepared by equilibration using acid catalysts. Anhydroustrifluoromethyl sulfonic acid in concentrations of about 0.l to 2.0weight per cent and concentrated sulfuric acid may be employedsuccessfully. The equilibration is generally run at temperatures ofabout 25 to 50C with vigorous stirring at least until the mixture hasbecome homogeneous. Said siloxane fluids can also be prepared byequilibration using a base catalyst. e.g. potassium silanolate. cesiumhydroxide and tetramethyl ammonium silanolate. Such catalysts arenormally employed in concentrations of 30-200 ppm as potassiumequivalent. The equilibration temperature depends on the catalystemployed. For instance. with tetramethyl ammonium silanolate atemperature of about to l00C. is sufficient. preferably about to C.,while the other alkaline catalysts usually require a temperature of atleast about l50C. Generally the equilibration time is less than 5 hours.Alternatively said siloxane fluids may also be prepared by the platiniumcatalyzed addition of an olefinic cyanide, eg. allyl cyanide to thecorresponding hydrosiloxane at temperatures of generally about 80 to90C. Such platinum catalysts and platinum derivatives are well known inthe art. chloroplatinic acid is particularly effective. The platinumcatalyst is conveniently employed as a solution for example intetrahydrofuran, ethanol, butanol or mixed solvents such asethanol-ethylene glycol dimethyl ether. The general preferredconcentration of platinum in the catalyst, based on the total weights ofsiloxane and olefinic derivatives, is about 5 to l00 parts per million,although higher and lower concentrations may be used. Solvents for thereaction e.g. benzene, toluene, xylene, ethers, and the like can be usedif desired. The preferred temperature range for the platinum catalyzedaddition process is generally from about 60 to lC. Lower temperaturesmay be used but the reaction times are slower. Higher temperatures mayalso be used e.g. up to 200C. but offer no apparent advantage. Thechoice of solvent if used should of course be adapted to the preferredtemperature range. The removal or neutralization of the platinum (e.g.chloroplatinic acid) catalyst is desirable for long range productstability. Usually sodium bicarbonate is added to the reaction mixtureto effect neutralization and the resultant slurry filtered. Of course itis preferred to use a stoichiometric excess of olefinic cyanide toinsure complete reaction of all of the silicon-hydrogen bonds.

The siloxane fluids containing hydrolyzable cyanoalkyl radicals(SiOR'CN) can be prepared by the catalyzed addition of cyano substitutedalkanols of the formula HOR'CN, e.g. HOC H CN, to the correspondinghydrosiloxanes. Said addition type process is conventional and can bepromoted by a variety of catalysts such as organic derivatives of tin,platinum and othere transition metals. Preferred are the organicderivatives of tin such as tin carboxylates, e.g. stannous octoate,stannous oleate, stannous laurate, dibutyl tin dilaurate and the like.The catalysts are generally used in amounts of about 0.1 to 5, usuallyno more than about 2, weight per cent, based on the total weight of there actants. The reaction temperature generally ranges from about 60 tol50C. (usually 80 to l20C.) Of course it is preferred to use astoichiometric excess of olefinic cyanide to insure complete reaction ofall of the silicon-hydrogen bonds.

The starting materials for the above processes as well as methods fortheir preparation are of course all well known in the art. It is to beunderstood, of course, that while the siloxane fluids used in thisinvention can be discrete chemical compounds they are usually mixturesof various discrete siloxane species, due at least in part, to the factthat the starting materials used to produce the siloxane fluids arethemselves usually mixtures. Thus it is to be also understood that theabove average formula representing the siloxane fluids as used hereinencompasses the presence of dihydrocarbon siloxanes as in the case ofunsparged equilibrated products and the possibility of the presence ofsmall amounts of other siloxy units, such as methyl (hydrogen) siloxygroups, in the siloxane polymers due to an incomplete reaction or thenature of the starting materials used to produce the siloxanes. Moreoverthe siloxane fluids employed herein need not be fractionated, as bydistillation but may be sparged (i.e. stripped of lites) or unsparged.

The amount of active cyanoalkyl modified siloxane employed as the foamstabilizer may fall within the range of about 0.03 to about 2 parts byweight or greater, per hundred parts by weight of the organic polyolstarting material. Preferably the siloxane fluids are employed inamounts ranging from about 0.08 to 0.6 parts by weight per 100 parts byweight of the organic polyol starting materials.

The polyhydroxyl reactants (organic polyols) employed in this inventionas the starting materials to prepare the polyurethane foams can be anypolyether triol containing at least 40 mole per cent of primary hydroxylgroups and having a molecular weight from about 2,000 to about 8,000.Conversely said polyether triols can contain no more than 60 mole percent of secondary hydroxyl groups. Preferably said polyether triolscontain about 60 to mole per cent of primary hydroxyl groups and have amolecular weight from about 4,000 to about 7,000.

The preferred polyether triols of this invention are polyalkyleneethertriols obtained by the chemical addition of alkylene oxides totrihydroxyl organic containing materials, such as glycerol;l,2,6-hexanetriol; l,ltrimethylolthane; l, l l -trimethylolpropane; 3-(2- hydroxyethoxy)- l ,2-propanediol; 3-( Z-hydroxypropyl l,Z-propanediol; 2,4-dimethyl-2 2- hydroxyethoxy )methylpentanedioll .5;l, l l-tris[ 2- hydroxy-ethoxy )methyl] ethane; l,l,l-tris[ 2-hydroxypropoxy)methyll-propane; and the like, as well as mixturesthereof.

Alternatively the organic polyol starting materials of this inventioncan be mixtures consisting essentially of said above defined polyethertriols and other polyether polyols having an average of at least twohydroxyl groups, said above defined polyether triols amounting to atleast 40 preferably at least 50, weight per cent of the total polyolcontent of the mixtures, Illustrative of such other polyethers aretriols outside of the scope defined above, diols, tetraols andpolymer/polyols, and the like, as well as mixtures thereof.

Examples of such polyether polyols that can be mixed with the abovedefined polyether triols include those adducts of alkylene oxide to suchpolyols as dicthylene glycol; dipropylene glycol; pentacrythritol;sorbitol; sucrose; lactose; alpha-methylglucoside;alphahydroxyalkylglucoside; novolac resins; water; ethylene glycol;propylene glycol, trimethylene glycol; l,2- butylene glycol;l,3-butanediol; l,4-butancdiol; 1,5- pentanediol; LIZ-hexane glycol;l,l0-decanediol; l,2- cyclohexanediol; 2-butene-l,4-diol;3-cyclohexenel, l -dimethanol; 4-methyl-3-cyclohexenel l dimethanol;3-methylenel ,S-pentanediol; (2-hydroxyethoxy l-propanol; 4( 2-hydroxyethoxy l-butanol; 5-( Z-hydroxypropoxy)-2-octanol; 3-allyloxyl,S-pentanediol; 2-allyloxymethyl-Z-methyl 1,3-propanediol;[4,4-pentyloxymethyl1- l ,B-propanediol;3-(o-propenyl-phenoxy)1,2-propanediol; 2,2-diisopropylidenebis(p-phenyleneoxy)diethanol; and the like, orphosphoric acid, benzenephosphoric acid; polyphosphoric acids such astripolyphosphoric acid and tetrapolyphosphoric acid; and the like; aswell as mixtures thereof.

Another type of polyether polyol that can be mixed with the abovedefined polyether triols and used as the starting materials of thisinvention are graft polymer/- polyether compositions obtained bypolymerizing ethyleneically unsaturated monomers in a polyether asdescribed in British Pat. No. 1,063,222 and US. Pat. No. 3,383,35l, thedisclosures of which are incorporated herein by reference thereto.Suitable monomers for producing such compositions include, for example,acrylonitrile, vinyl chloride, styrene, butadiene, vinylidene chloride.and the like. Suitable polyethers'for producing such compositionsinclude, for example those polycthers hereinabove-described. These graftpolymer/polyether compositions can contain from about l to about 70weight per cent. preferably about to about 50 weight per cent and mostpreferably about l0 to about 40 weight per cent of the momomerpolymerized in the polyether. Such compositions are conve nientlyprepared by polymerizing the monomers in the selected polyether at atemperature of 40 to 150C. in the presence of a free radicalpolymerization catalyst. such as peroxides. persulfates. percarbonates.perborates and azo compounds as more fully described by the above patentreferences. The resulting compositions may contain a small amount ofunreacted polyether. monomer and free polymer as well as the graftpolymer/polyether complex. Especially preferred are the graftpolymer/polycthers obtained from acrylonitrile and polyether triols.

The alkylene oxides employed in producing the preferred polycthersdescribed above normally have from 2 to 4 carbon atoms, inclusive whilepropylene oxide and mixtures of propylene oxide and ethylene oxide areespecially preferred.

The exact organic polyol or polyols employed as the starting materialsof this invention merely depend on the end use of the high resiliencepolyether urethane foam. For instance. the employment of polyethertriols having at least 40 mole per cent primary hydroxyl groups andmolecular weights from 2.000 to 8.000

preferably 4.000 to 7.000 generally have hydroxyl numbers from 84 to 2i.preferably 42 to 28 and give primarily flexible polyether foams. Thesupplementary polycthers which may have any proportion of primary tosecondary hydroxyl groups and which may be mixed with the requiredpolyether triols can be used to control the degree of softness of thefoam or vary the load bearing properties of the foam. Such limits arenot intended to be restrictive, but are merely illustrative of the largenumber of possible combinations of polyether triols and other polycthersthat can be employed.

The hydroxyl number is defined as the number of milligrams of potassiumhydroxide required for the complete neutralization of the hydrolysisproduct of the fully acetylated derivative prepared from 1 gram ofpolyol or mixtures of polyols with or without other crosslinkingadditives used in the invention. The hydroxyl number can also be definedby the equation:

wherein OH hydroxyl number of the polyol.

A variety of organic isocyanates can be employed in the foamformulations of this invention for reaction with the organic polyolstarting materials above described to provide high resilience polyetherurethane foams. Preferred isocyanates are polyisocyanates andpolyisothiocyanates of the general formula:

wherein Y is oxygen or sulfur, i is an integer of two or more and O isan organic radical having the valence of i. For instance, 0 can be asubstituted or unsubstituted hydrocarbon radical, such as alkylene andarylene. having one or more aryl-NCY bonds and/or one or more alkylNCYbonds. 0 can also include radicals such as QZQ where O is an alkylene orarylene group and Z is a divalent moiety such as O. OQO.

CO. CO -S. -SOS, SO and the like. Examples of such compounds includehexamethyl diisocyanate. l.8-diisocyanato-p-methane, xylylenediisocyanate. (OCNCH CH CH OCH O, l-methyl-2.4- diisocyanatocyclohexane,phenylene diisocyanates. tolylene diisocyanates, chlorophenylenediisocyanates. diphenylmethane4.4'-diisocyanate, naphthalene-1,5-diisocyanate, triphenylmethane-4,4'-4"-triisocyanate. andisopropylbenzene-alpha-4-diisocyanates.

Further included among the isocyanates useful in this invention aredimers and trimers of isocyanates and diisocyanates and polymericdiisocyanates such as those having the general formula:

(Q M and [Q( )ilJ in which i andj are integers of two or more. and/or(as additional components in the reaction mixtures) compounds of thegeneral formula:

in which i is one or more and L is a monofunctional or polyfunctionalatom or radical. Examples of this type include ethylphosphonicdiisocyanate. C H P(O) (NcOlg; phenylphosphonic diisocyanate. C..H;.P(O)(NCOJ- compounds containing a SiNCO group. isocyanates derived fromsulfonamides (OSO NCO). cyanic acid. thiocyanic acid. and compoundscontaining a metal NCO radical such as tributyltinisocyanate.

More specifically. the polyisocyanate component employed in thepolyurethane foams of this invention also includes the followingspecific compounds as well as mixtures of two or more of them:2.4-tolylene diisocyanate. 2.6-tolylene diisocyanate, crude tolylenediisocyanate. bis(4-isocyanatophenyl)methane. polymethylenepolyphenylisocyanates that are produced by phosgenation ofanilineformaldehyde condensation products. dianisidine diisocyanate.toluidine diisocyanate. xylylene diisocyanate. bis( 2-isocyanatoethyl)-fumarate. bis(Z-isocyanatoethyl) carbonate. l.6-hexamethylene-diisocyanate. l .4tetramethylenediisocyanate.l.l0-deca-methylene-diisocyanate. cumene-ZA-diisocyanate.4-methoxy-1.3-phenylene diisocyanate 4-chlorol .3-phenylenediisocyanate.4bromol .3-phenylene diisocyanate. 4-ethoxy-l .3-pheriylene-diisocyanate 2 4'-diisoeyanatodiphenylether.5.6-dimethyl-l.3-phenylene diisocyanate.2.4-dimethyl-l.3-phenylenediisocyanate. 4.4- diisocyanatodiphenylether.bis 5.6-(2-iso-cyanatoethylibicyclo [2.2.1 ]hept-2-enebenzidinediisocyanate. 4.6-dimethyll .3-phenylenediisocyanate. 9. l 0-anthracenediisocyanate. 4.4-diisocyanatodibenzyl. 3.-3-dimethyl-4,4'-diisocyanatodiphenylmethane. 2.6dimethyl-4.4'-diisocyanatodiphenyl 2.4- diisocyanatostilbene.3.3'-dimethyl-4.4'- diisocyanatodiphenyl. 3,3'-dimethoxy4.4'-diisocyanatodiphenyl l.4-anthracenediisocyanate. 2.5-fluorenediisocyanate l,S-naphthalenediisocyanate.2.o'diisocyanatobenzfuran. 2.4.o-toluenetriisocyanate, and many otherorganic polyisocyanates that are known in the art. such as those thatare disclosed in an article by Siefken. Ann.. 565. (i949). In general.the aromatic polyisocyanates are preferred.

Particularly useful isocyanate components of high resilience cold cureformulations within the scope of this invention are combinations ofisomeric tolylene diisocyanates and polymeric isocyanates having unitsof the formula wherein R is hydrogen and/or lower alkyl and x has avalue of at least 2.1. Preferably the lower alkyl radical is methyl andx has a value of from 2.1 to about 3.0.

The amount of polyisocyanate employed will vary slightly depending onthe nature of the polyurethane being prepared. in general thepolyisocyanates are employed in the foam formulations of this inventionin amounts that provide from 80 to 150 per cent, preferably from 90 to110 per cent of the stoichiometric amount of the isocyanato groupsrequired to react with all of the hydroxyl groups of the organic polyolstarting materials and with any water present as a blowing agent. Mostpreferably, a slight amount of isocyanato groups in excess to thestoichiometric amount is employed.

The blowing agents employed in this invention include methylenechloride, water, liquefied gases which have boiling points below 80 andabove -60F., or by other inert gases such as nitrogen, carbon dioxide,methane, helium and argon. Suitable liquefied gases include saturatedaliphatic fluorohydrocarbons which vaporize at or below the temperatureof the foaming mass. Such gases are at least partially fluorinated andcan also be otherwise halogenated. F luorocarbon blowing agents suitablefor use in foaming the formulations of this invention includetrichloromonofluoromethane, dichlorodifluoromethane,dichlorofluoromethane, l, l chlorol -fluoroethane, l-chlorol l-difluoro, 2,2- dichloroethane, and [,1 ,l ,-trifluoro,2-chloro-2-fluoro, 3,3-difluoro-4,4,4-trifluorobutane. The amount ofblowing agent used will vary with density desired in the foamed product.Usually from 2 to 20 parts by weight of the blowing agent per parts byweight of the organic polyol starting materials are preferred.

The catalysts employed in this invention include any of the catalystused in producing conventional flexible polyurethane foam. Illustrativecatalysts are conventional amine catalysts such as N-methyl morpholine,N-ethyl morpholine, hexadecyl dimethylamine, trieth ylamine,N,N,N'N'-tetramethyl-l ,3-butanediamine, N,N-dimethylethanol-amine,bis(2-dimethylaminoethyl)ether, N,N,N',N'-tetramethyl ethylenediamine,4,4-methylene bis(2-chloroaniline), dimethyl benzylamine, N-cocomorpholine, triethylene diamine, l,4- diazobicyclo (2,2,2)-octane], theformate salts or triethylene diamine, other salts of triethylene diamineand oxyalkylene adducts of primary and secondary amino groups, and thelike. If desired, conventional organo metal catalysts may be used tosupplement the amine catalysts. Illustrative of such metal catalysts arethe tin salts of various carboxylic acids e.g. stannous octoate, dibutyltin dilaurate, nickel acetylacetonates, and the like. Generally thetotal amount of catalyst employed in the mixtures will range from 0.l to2 weight per cent based on the total weight of the organic polyolstarting materials.

The relative amounts of the various components reacted in accordancewith the above described process for producing high resilience polyetherurethane foams in accordance with this invention are not narrowlycritical. The polyether and the polyisocyanate are present in the foamformulations used to produce such foams, Le. a major amount. Therelative amounts of these two components is the amount required toproduce the urethane structure of the foam and such relative amounts arewell known in the art. The blowing agent, catalyst and siloxanes areeach present in a minor amount necessary to achieve the function of thecomponent. Thus, the blowing agent is present in a minor amountsufficient to foam the reaction mixture, the catalyst is present in acatalytic amount (i.e., an amount sufficient to catalyze the reaction toproduce the urethane at a reasonable rate) and the siloxane fluids arepresent in a foam-stabilizing amount (i.e., in an amount sufficient tostabilize the foam against voids and shrinkage). Pre ferred amounts ofthese various components are given hereinabove.

The high resilience cold cure urethane foams produced in accordance withthis invention can be used for the same purposes as correspondingconventional hot cure polycther urethane foams, c.g. they can be usedwhere ever cushioning is desired, e.g. in furniture; in transportationsystems, automobiles, planes, etc; in carpeting; in the packaging ofdelicate objects; and the like.

Other additional ingredients can be employed in minor amounts inproducing the high resilience polyether urethane foams in accordancewith the process of this invention, if desired, for specific purposes.Thus inhibitors (e.g. d-tartaric acid and tertiary-butyl pyrocatechol,lonol") can be employed to reduce any tendency of the foam to hydrolyticor oxidative instability. Flame retardants (cg. tris(Z-chloroethyl)phosphate) can be used. Dihydrocarbon silicone oils, cg.dimethylsiloxanes, the siloxane-oxyalkylene block copolymers describedin US. Pat. Application No. 84,l8l filed Oct. 26, 1970 and the aralkylmodified siloxanes described in Us. Pat. Application No. 305,713 filedNov. 13, 1972 may be mixed if desired with the siloxanes employed inthis invention. While such mixtures are not required they may helpexpand the usefulness of the siloxane fluids employed herein byincreasing the adaptability of the siloxane fluid to a variety of foamformulations. Of course any organic solvent for the amine catalysts,e.g. polyols such as hexylene glycol (Le. 2-methyl-2 4-pentanediol),dipropylene glycol, and the like can be used which substantially do notadversely effect the operation of the process or reactants. Examples ofother additives that can be employed are crosslinkers such as glycerol,triethanol amine, and their oxyalkylene adducts, and anti-yellowingagents.

An additional feature of the instant invention are the novelcompositions suiable for use in producing the high resilience polyetherurethane foam. For example it may be desirable, particularly on acommercial scale to employ the cyanoalkyl modified siloxane fluid in adiluted form, i.e. in the form of a siloxane fluid-solvent solutionpremix or a siloxane fluid-solvent-catalyst solution premix. Suchsolution premixtures can help serve to eliminate any mixing, metering,or settling problems. Moreover, fewer streams of ingredients may beneeded at the mixing head of the operational apparatus. Of considerableimportance is that the formula tor has the latitude to select theparticular solvent which best suits the system and minimize or eliminateany loss of foam properties. Siloxane fluid-solventcatalyst premixes canalso be used since the selected solvent can be one which serves the dualrole of solvent for the catalysts as well as the siloxane fluid. Thisoption of formulating a premix simplifies the foaming operation andimproves the precision of metering ingredients. While any suitableorganic solvent such as hydrocarbon. halohydrocarbons, organic hydroxylcompounds, alkyl phthalates. and the like may be employed, preferablywhen employed the solvent selected should be one in which the cyanoalkylmodified siloxane fluid is substantially soluble. For example, it ispreferred that at least five parts by weight of the cyanoal kyl modifiedsiloxane oil be soluble in 95 parts by weight of solvent. Morepreferably the minimum pcrcentage of cyanoalkyl modified siloxane fluidin the siloxane fluid-solvent or siloxane fluid-solvent-catalystsolutions should be in the range of at least about ten to at least aboutweight percent. Of course it is understood that such solvents need notbe employed and that the maximum percentage of cyanoalkyl modifiedsiloxane fluid in said solvent solutions is not critical. Moreover. whenemployed such solvent solutions should of course be correlated to theamounts of active cyanoalkyl modified siloxane fluid that may beemployed per hundred parts by weight of the organic polyol startingmaterial as outlined above. The same correlation should also be madewith regard to catalyst when a siloxane fluid-solvent-catalyst solutionis employed. Preferably the solvent for the cyanoalkyl modified siloxanefluid is an organic hydroxyl compound such as hydroxyl terminatedorganic ether compounds. More preferably they are polyether triols,diols. and mono-ols such as the adducts of ethylene oxide, propyleneoxide. butylene oxide, with starters such as glycerol. water,trimethylolpropane. l.2.6-hexanetriol. ethylene glycol. butanol,nonylphenol. and the like. Of course the oxyalkylene units of suchadducts may be of different types. eg oxypropylene and oxyethylenegroups. and may be randomly distributed or in blocks. The most preferredsolvents are the polyether triols having all or predominantlyoxypropylene units in the oxyalkylene portion and having molecularweights in the range from about 2.000 to 6.000 inasmuch as they may bethe same. as or similar to the primary triols employed as the organicpolyol starting material of the foam formulation. Moreover thisdiscovery concerning the solubility of the cyanoalkyl modified siloxanefluids of this invention can be regulated and controlled. For stabilityrea sons it is preferred to use the siloxane fluids containingnon-hydrolyzable cyanoalkyl radicals (Si-R 'CN) in said solventsolutions.

In accordance with this invention, the cold cure polyether urethanefoams can be produced by any suitable technique. The preferred processis a one-step or one shot technique wherein all of the reactants arereacted simultaneously with the foaming operation. A second generalprocess is called the prepolymer process whereby a prepolymer is formedby reacting the poly ether starting material with a small excess of theisocyanate and later foaming the prepolymer by the reaction with wateror an inert blowing agent. Another method which can be used is thequasi-prepolymer technique which involves reacting a large excess of theisocyanate with the polyether starting material and then subsequentlyfoaming this product with additional polyether in the presence of ablowing agent. Of course it is understood that the ingredients of thefoam forming formulation can be mixed in any suitable manner prior tocommencing the cure reaction. Sometimes it is preferred to employvarious premixes such as a premixture of the polyether starting materialand siloxane fluid stabilizer; a premixture of polyether startingmaterial, siloxane fluid, water and catalyst; a premixture of thepolyisocyanate and siloxane fluid, a siloxane fluidsolvent-catalystsolution as outlined above; and the like. Because of the high exothermicnature of the reaction high resilience urethane foams are rapidlyproduced without the need of any external heat by mixing the reactantsat ambient temperatures and pouring the foaming reaction mixture into asuitable mold and following the foam to cure itself. Of course, ifdesired the overall reaction can be even further accelerated bypreheating the mold and/or employing conventional high temperature postcuring procedures. Within a shorter period of time the cold cureprocess. with or without post cure, simultaneously achieves a greaterdegree of cure throughout the entire foam, and shorter tack free anddemolding time, then is generally achieved with conventional hot cureprocesses. For instance, cold cure foams can be removed from the moldfar sooner without substantial damage to the surface than conven tionalhot cure foams. Of course it is to be understood that the highresilience polyether urethane foam of this invention can also beprepared in slabstock form, if desired.

The following examples illustrate the present invention and are not tobe regarded as limitative. It is to be understood that the averageformulas of the siloxane fluid products are based on the mole ratios ofthe starting materials employed, Me represents a methyl radical. Conc."represents concentration. p.h.p. refers to parts of siloxane-solventsolution per hundred parts of organic polyol starting material unlessotherwise designated. lOO Index indicates that the number of moles ofNCO groups is equal to the total moles of hydroxyl groups in the foamformulation. one drop of tetramethylammonium silanolate is equivalent to4.57 ppm as K, and that all of the parts, percentages and proportionsreferred to herein and in the appended claims are by weight unlessotherwise indicated.

EXAMPLE 1 Into a flask equipped with a thermometer. mechanical stirrer,condenser and nitrogen blow-by were charged about l3.5 grams ofhexamethyldisiloxane, about 42.5 grams of a cyclicgamma-cyanopropylmethylsiloxane having a viscosity of about (1l7centistokes at 25C., about l9 grams of cyclic dimethylsiloxane tetramer,and about 21 drops of tetramethyl ammonium silanolate catalyst (l28 ppmas K). The mixture was then equilibrated with stirring under a nitrogenblanket for 2 hours at C., followed by an additional 1 9% hours at C. todeactivate the catalyst, then cooled and filtered. There was obtained aclear cyanoalkylmodified siloxane fluid product having the averageformula Me SiO( Me- SiO NC(CH siMeOl siMe Said siloxane has an averagemolecular weight of about 898, a viscosity of about 47.9 centistokes at25C., a siloxane content of about 69.7 wt. 70, and is hereinafterreferred to as Siloxane I.

EXAMPLE 2 Example 1 was repeated except about 14.2 grams ofhexamethyldisiloxane, about 38.3 grams of the cyclicgamma-cyanopropyl-methylsiloxane and about 22.5 grams of cyclicdimethylsiloxane tetramer were used and the reaction maintained at 90C.for 1 V2 hours followed by an additional 1 V2 hour at 150C. There wasobtained a clear cyanoalkyl-modified siloxane fluid having the averageformula Said siloxane has an average molecular weight of about 857, aviscosity of about 36.9 centistokes at 25C., a siloxane content of about72.7 wt. and is hereinafter referred to as Siloxane ll.

EXAMPLE 3 Example 1 was repeated except about 14.7 grams ofhexamethyldisiloxane, about 34.8 grams of the cyclicgamma-cyanopropyl-methylsiloxane, about 25.5 grams of cyclicdimethylsiloxane tetramer, and about 7 drops of the tetramethyl ammoniumsilanolate catalyst 43 ppm as K) were used. The reaction was maintainedat 90C. for 2 hours followed by an additional 1 V2 hour at 150C. Therewas obtained a clear cyanoalkylmodi fled siloxane fluid having theaverage formula Said siloxane has an average molecular weight of about827, a viscosity of about 31.4 centistokes at 25C., a siloxane contentof about 75.1 wt. 71, and is hereinafter referred to as Siloxane 111.

EXAMPLE 4 Example 1 was repeated using about 17.4 grams ofhexamethyldisiloxane, about 34.3 grams of the cyclicgarnma-cyanopropyl-methylsiloxane and about 23.3 grams of cyclicdimethylsiloxane tetramer and the reaction maintained at 90C. for 2 V2hours followed by an additional 3 hours at 150C. There was obtained aclear cyanoalkyl-modified siloxane fluid having the average formula Saidsiloxane has an average molecular weight of about 700, a viscosity ofabout 22.4 centistokes at 25C., a siloxane content of about 75.5 wt. andis hereinafter referred to as Siloxane 1V.

EXAMPLE 5 Example 1 was repeated except about 18.3 grams ofhexamethyldisiloxane, about 35.8 grams of the cyclicgamma-cyanopropyl-methylsiloxane and about 20.9 grams of cyclicdimethylsiloxane tetramer were used and the reaction maintained at 90C.for 1 V2 hours followed by an additional 1 /1 hours at 150C. There wasobtained a clear cyanoalkyl modified siloxane fluid having the averageformula Said siloxane has an average molecular weight of about 665, aviscosity of about 21.6 centistokes at 25C., a siloxane content of about74.4 wt. 71, and is hereinafter referred to as Siloxane V.

EXAMPLE 6 Example 1 was repeated except about 21.9 grams ofhexamethyldisiloxane, about 30.1 grams of the cyclicgamma-cyanopropyl-methylsiloxane, about 23 grams of cyclicdimethylsiloxane tetramer, and about 14 drops of the tetramethylammonium silanolate catalyst ppm as K) were used. The reaction wasmaintained at C. for 1 V2 hours followed by an additional 1 A hour at C.There was obtained a clear cyanoalkylmodified siloxane fluid having theaverage formula Said siloxane has an average molecular weight of about554, a viscosity of about 12.8 centistokes at 25C., a siloxane contentof about 78.5 wt. 7:, and is hereinafter referred to as Siloxane V1.

EXAMPLE 7 Example 5 was repeated except about 22.7 grams ofhexamethyldisiloxane, about 26.5 grams of the cyclicgamma-cyanopropyl-methylsiloxane and about 25.8 grams of cyclicdimethylsiloxane tetramcr were used. There was obtained a clearcyanoalkyl-modified siloxane fluid having the average formula Saidsiloxane has an average molecular weight of about 538, a viscosity ofabout 9.8 centistokes at 25C., a si loxane content of about 81 wt. "/1and is hereinafter referred to as Siloxane V11.

EXAMPLE 8 Example 5 was repeated except about 27.8 grams ofhexamethyldisiloxane, about 21.8 grams of the cyclicgamma-cyanopropyl-methylsiloxanc and about 25.4 grams of cyclicdimethylsiloxane tetramer were used. There was obtained a clearcyanoalkyl-modifled siloxane fluid having the average formula Saidsiloxane has an average molecular weight of about 437, a viscosity ofabout 6.4 centistokes at 25C., a siloxane content of about 84.4 wt. 9?,and is hereinafter refered to as Siloxane Vlll.

EXAMPLE 9 Said siloxane has an average molecular weight of about 545, aviscosity of about 9.9 centistokes at 25C., a siloxane content of about80 wt. "/1, and is hereinafter referred to as Siloxane lX.

EXAMPLE 10 Example l was repeated except about 1 1.8 grams ofhexamethyldisiloxane. about 55.7 grams of the cyclicgamma-cyanopropyl-methylsiloxane about 32.5 grams of the cyclicdimethylsiloxane tetramer, and about 28 drops of the tetramethylammonium silanolate catalyst U28 ppm as K) were used. The reaction wasmaintained at 9095C. for 4 hours followed by heating at 150C. for anadditional 2 hours. Upon cooling and filtering there was obtained aclear cyanoalkyl-modified siloxane fluid having the average formula Saidsiloxane has an average molecular weight of about l368, a viscosity ofabout 99.4 centistokes at 25C., a siloxane content of about 70.6, and ishereinafter referred to as Siloxane X.

EXAMPLE l l Into a 25G ml. three-necked flask equipped with athermometer, mechanical stirrer, condenser and nitrogen blow-by werecharged about l6.2 grams (0.! mole) of hexamethyldisiloxane(Me;.SiOSiMe;,), about 29.6 grams (0.4 mole) of cyclic dimethylsiloxanetetramer HMe SiOhl. and about 35.6 grams (0.28 mole) of a cyclicgammacyanopropyl'mcthylsiloxane lNCtCH- hsiMeol having a viscosity ofabout 2 l() centistokes at 25C. The mixture was then equilibrated undera nitrogen blanket by stirring it vigorously at room temperature while0.75 weight percent (0.61 grams) of trifluoromethane sulfonic acidcatalyst was added to the system. Agitation was maintained for If hours.At this time an additional 0.025 weight percent of more trifluoromethanesulfonic acid was added and the mixture became homogeneous within 2hours. Equilibration was continued for 4 more hours at room temperature.The equilibrated product was neutralized with about grams of sodiumbicarbonate and filtered. There was obtained a clearcyanoall-tyl-rnodifled siloxane fluid product having the average formulaMe siOtMc siOt JNC(CH );,SiMeO] ,.SiMe Said siloxane has an averagemolecular weight of about M4, a viscosity of about 35.8 centistokes atC. a siloxane content of about 76.6 wt. 9?, and is hereinafter referredto as Siloxane Xl.

EXAMPLE l2 Example I l was repeated except about 65 grams ofhexamethyldisiloxane. about 89 grams of cyclic di' mcthylsiloxanetetramer. about 76 grams of the cyclic gamma-cyanopropyl-methylsiloxanewere used along with increments of about l.l5 grams and 0575 grams ofthe trifluoromethane sulfonic acid catalyst and about grams of sodiumbicarbonate to neutralize the equilibrated product. There was obtained aclear cyanoalkyl-modifled siloxane fluid product having the averageformula Me;,SiO( Me SiOMNC(CH );;SiMeO] SiMe Said siloxane has anaverage molecular weight of about 575. a viscosity of about 17.0centistokes at 25C., a siloxane content of about 82 wt. /1 and ishereinafter referred to as Siloxane Xll.

EXAMPLE 13 Example 6 was repeated except about 33.5 grams ofhexamethyldisiloxane, about 26.2 grams of the cyclicgarnma-cyanopropyl-methylsiloxane and about l5.3 grams of cyclicdimethylsiloxane tetramer were used. There was obtained a clearcyanoalkylmodifled siloxane fluid having the average formula Saidsiloxane has an average molecular weight of about 363. a viscosity ofabout 5 centistokes at 25C., a siloxane content of about 8 l .3 wt. /1,and is hereinafter referred to as Siloxane XllI.

EXAMPLE l4 Example 6 was repeated except about 4.8 grams ofhexamethyldisiloxane, about 37.5 grams of the cyclicgamma-cyanopropylmethylsiloxane and about 32.7 grams of cyclicdimethylsiloxane tetramer were used. There was obtained a clearcyanoalkyl-modified silox ane fluid having the average formula Saidsiloxane has an average molecular weight of about 2542, a viscosity ofabout loo ccntistokes at 25C.. a siloxane content of about 73.2 wt. 4and is hereinafter referred to as Siloxane XIV.

EXAMPLE l5 Example 1 was repeated except about 5.6 grams ofhexamethylclisiloxane, about 43.9 grams of the cyclicgamma-cyanopropyl-mcthylsiloxane and about 25.5 grants of cyclicdimethylsiloxane tetramcr were used and the reaction maintained at 9UC.for 2 /2 hours, at [00C. for A: hour. at l 10C. for one-half hourfollowed by an additional hour at l5t)C. There was obtained a clearcyanoalkyl-modifled siloxane fluid having the average formula Mc3SiO(MCgSiO u iNC(CH3)3SiMCO] SiMC Said siloxane has an average molecularweight of about 2 l72. a viscosity of about 220 centistokes at 25C.. asiloxane content of about 68.7 wt. and is hereinafter referred to asSiloxane XV.

EXAMPLE lo Into a flask equipped with a thermometer, mechanical stirrer.condenser and nitrogen blow-by were charged about l62 grams ofhexamethyldisiloxane about 95.8 grams of a cyclic gammacyanopropylmethylsiloxane having a viscosity of about 6| 7 centistokes at 25C.. about1783 grams of cyclic dimethylsiloxane tetramer. and about 2 weight percent of concentrated H catalyst. The mixture was then equilibrated withstirring under a nitrogen blanket for about 4 hours at 4U-45C.. thenneutralized with sodium bicarbonate and filtered. There was obtained aclear cyanoalkylmodified siloxane fluid product having the average formula Me siOt Me SiO NC( CH SiMeO l SiMe Said siloxane has an averagemolecular weight of about 436. a viscosity of about 4.6 centistokes at25C.. a siloxane content of about 88.2 wt. 9%, and is hereinafterreferred to as Siloxane XVI and represents a siloxane of this invention.

EXAMPLE 17 Into a flask equipped with a thermometer. mechanical stirrer,condenser and nitrogen blow-by were charged about I62 grams ofhexamethyldisiloxane, about 82.6 grams of a cyclicgamma-cyanopropylmethylsiloxane having a viscosity of about 617centistokes at 25C., about 195.4 grams of cyclic dimethylsiloxanetetramer, and about 2 weight percent of concentrated H 80 catalyst. Themixture was then equilibrated with stirring under a nitrogen blanket forabout 4 hours at 4045C., then neutralized with sodium bicarbonate andfiltered. There was obtained a clear cyanoalkylmodified siloxane fluidproduct having the average formula Said siloxane has an averagemolecular weight of about 440, a viscosity of about 4.6 centistokes at25C., a siloxane content of about 90 wt. and is hereinafter referred toas Siloxane XVII and represents a siloxane of this invention.

EXAMPLE l8 Into a flask equipped with a thermometer, mechanical stirrer.condenser and nitrogen blow-by were charged about l62 grams ofhexamethyldisiloxane, about I08 grams of a cyclicgamma-cyanopropylmethylsiloxane having a viscosity of about 6 l 7centistokes at 25C., about 222 grams of cyclic dimethylsiloxanetetramer, and about 2 weight per cent of concentrated H 80 10 grams)catalyst. The mixture was then equilibrated with stirring under anitrogen blanket for about 4 hours at 4045C., then neutralized withsodium bicarbonate and filtered. There was obtained a clearcyanoalkylmodified siloxane fluid prroduct having the average formulaSaid siloxane has an average molecular weight of about 490, a viscosityof about 5.3 centistokes at C. and is hereinafter referred to asSiloxane XVIII and repre sents a siloxane of this invention.

EXAMPLE l9 Example l8 was repeated except about 13.5 grams of thehexamethyldisiloxane. about 42.5 grams of the cyclicgamma-cyanopropylmethylsiloxane, and 178 grams of the cyclicdimethylsiloxane tetramer were used. There was obtained a clearcyanoalkyl-modifled siloxane fluid product having the average formulahaving an average molecular weight of about 530 and is hereinafterreferred to as Siloxane XIX and represents a siloxane of this invention.

For the sake of brevity the above designations given for the siloxanefluids along with the following designations are used to denote thevarious ingredients employed in the following examples.

TABLE I Designation Organic Polyols Composition l This is a polyethertriol mol. wt. about 6,000; hydroxyl No. about 27; containing aboutTABLE l-Continued Des ignat io n Organic Polyols Composition 85 mole /lprimary hydroxyl groups produced by reacting about 89% propylene oxideand about I l7! eth lene oxide with glycerol.

This is a polyether triol,

mol. wt. about 5,000; hydroxyl No. about 34; containing about mole '1:primary hydroxyl groups produced by reacting about 84% propylene oxideand about lo /z ethylene oxide with glycerol.

This is a graft polymcr/ polyol; about wtfi; polyoL ltl wtft styrene andIt) wtf/r acrylonitrile; having a hydroxyl No. of about 28, produced bypolymerizing styrene and acrylonitrile in E2. Composition This is amixture of about 80 wt.'/: 2.4-tolylcnc diisocyanatc and about 20 wL /4lb-toluene diisocyanatc.

This is a polymethylcnc polyphenyl isocyanate polymer containing about2.6 2.9 moles of NCO per mole of polymer and having an isocyanatccontent of about 3 l .4 per cent. This is a composition of about Ht)wtf/i (l and about 20 1M ('2.

Composition This is a composition consisting of about 71) wtfii bisl NN-dimcth slnminocthyl] ether and about 31) 1.0; Llipropylcnc glycolsolvent. Composition This is a polyether triol.

mol. wt. about 3000 produced by reacting propylene oxide with glyceroland a hydroxyl number of about 56.

Polyisocyanates C 1 Catalyst Al Siloxane Solvents Sl EXAMPLE 2() Thefoam formulations employed in producing the foams in this example wereidentical save for variations in the amount of cyanoalkyl modifiedsiloxane fluid employed. The high resilience polyether urethane foamswere all prepared and evaluated in the following manner.

A blend of polyether triols E2 and E3 was dispersed into a paper cup atabout 20 to 30C. Then the siloxane fluid and dibutyltimdilauratecatalyst were added via a 5 cc syringe and dispersed with a spatulafollowed by a premix of water, Al catalyst, solid triethylene diamineand N-ethylmorpholine catalyst which was also dispersed in the mixturewithout using a baffle. The mixture was then placed under a drill pressmixer and agitated for about 10 seconds at 2.150 rpm, while the cup wasturned around to insure proper mixing. Without stopping the drill presspolyisocyanate C3 was rapidly added and mixed for about seven seconds.The foam forming mixture was then rapidly poured into an 8 X 8 X 6inches parchment lined cake box which was supported by a wooden mold andallowed to cure. The high resilience polyether urethane foam product wasallowed to rest for at least two minutes after completion of the foamrise to avoid densiflcation at the bottom of the foam bun. Thereafterthe foam while still in the cake box was placed in an oven at l25C. forabout ten minutes to reduce tackiness and facilitate separation of thepaper liner from the mold and cutting of the foam samples. The foam wasallowed to stand for about I hour before cutting when it was then sliced1 V2 inches from the bottom with a band saw.

a 2 X 2 X 1 inches piece of foam cut from near the center of the bunusing a Nopco Foam Breathability Testcr. GP-2 Model 40 GD l0. Air isdrawn through the l inch portion at a pressure differential of 0.5inches of Said foam formulations all contained 100 parts by 5 water lessthan atmospheric pressure. The air flow is weight of the polyether blendon the order of about 60 parallel to the direction of original foamrise. The departs (I5 grams) of polyether triol E2 and 40 parts gree ofopenness of the foam (or foam breathability) is I00 g of p ly t r triolabout pa t by measured by air flow and is designated in standard weight(6.5 grams) of water; about 0.l parts by weight ubi feet er minute.

TABLE 2 Foam Siloxane Siloxane Solution Foam ells/ No. Fluid No. Cone.(php) Breath-ability Inch Shrinkage Ccll Uniformity A (ontrol None 4.7lb Nonc Severe Voids Irregular I I 0.3 6.5 22 None Severe VoidsIrregular 2 l 0.75 6.l 24 None Moderate Voids Irregular 3 l I II 8.5 24None No Voids Uniform 4 ll 0.] 6.2 22 None Slight Voids Irregular 5 II0.75 7.5 24 None No Voids Uniform 6 II 1.12 13.2 26 None No VoidsUniform 7 III 0.3 7.8 24 None No Voids Uniform 8 III 0.75 I l I 22 NoneNo Voids Uniform 9 III l I2 I83 28 None No Voids Uniform III IV I) 3 8.524 None Slight Voids Irregular I I I\ 0.75 8.7 26 None No Voids UniformI2 IV I.I2 I0 7 28 None No Voids Uniform I} V 0 3 9.0 24 None SevereVoids Irregular l4 V 0.75 9 I 26 None No Voids Uniform I5 V l.l2 7.) 26None No Voids Uniform in VI 0.3 8.5 24 None Moderate Voids Irregular l7VI 0.75 7.3 24 None No Voids Uniform I8 VI I.I2 J 5 24 None No VoidsUniform I) VII 0.3 7.6 24 None Slight Voids Irregular 2t) \II (I 75 8.626 None No Voids Uniform 2| VII 1. I2 I I." 28 None No Voids Uniform 21VIII ll 3 7.6 22 None Slight Voids Irregular 33 VIII 0 75 9.3 24 None NoVoids Uniform 24 VIII I. II 9.4 24 None No Voids Uniform IX I.I2 7.1 26None No Voids Uniform If! X 0.375 6.9 24 None No Voids Uniform 27 X 0.75I54 2: None Slight Voids Irregular 28 XI 0.I 0.75 32 None No VoidsUniform Z9 XII 0.1 1.05 4 None No Voids Uniform Siloxanes Not of ThisImention 30 XII] l. 12 7 4 20 None Severe Voids Irregular 3l XIII 3.257.6 22 None Severe Voids Irregular 32 XIV 0.3 Seven: No Voids Uniform 33XIV 0.75 f Severe No Voids Uniform 34 XV 0.3 v Severe No Voids Uniform35 XV 075 Severe No Voids Uniform Lvaluatcd as lll0 per cent aelhesilomnc fluld (no v'ol\ cull (0.25 grams) of amine catalyst Al; aboutI.2 parts by weight (3.0 grams) of N-ethylmorpholine catalyst; about 0.I 2 parts by weight (0.3 grams) of solid triethylene diamine catalyst;about 0.0l5 parts by weight (0.038 grams) of dibutyltindilauratecatalyst and about 33.9 parts by weight 84.8 grams) of polyisocyanate C3(I00 Index). The cyanoalkyl modified siloxane fluid was used in the formof a siloxane fluid-solvent solution composed of about 22 parts byweight of siloxane fluid and 78 parts by weight of solvent SI unlessotherwise noted. The amount and particular siloxane fluid employed wasvaried and the recorded properties of the various foam samples are givenin TABLE 2 below.

The breathability measurements, except for Foam Nos. 28 and 29 were allrecorded by a Gurley Densometer which measures the porosity or airresistance of the foam as shown by the time in seconds for a givenvolume of air (300 ccs of air) to pass through I square inch of foam.The value recorded is the average value of live such measurements givenin seconds per 300 ccs of displaced air. The breathability measurementsof Foam Nos. 28 and 29 denote the porosity of the foam and is roughlyproportioned to the number of open cells in the foam. They were measuredby taking EXAMPLE 2l Another series of high resilience polyctherurethane foam was produced in the same manner as Example 20 except thatthe foam formulations all contained I00 parts by weight of the polyetherblend on the order of about 50 parts I00 grams) of polyether triol Eland about 50 parts I00 grams) of polyether triol E3; about 2.7 parts(5.4 grams) of water; about 008 parts (0. l6 grams) of amine catalystAl; about 0.8 parts of N- ethylmorpholine catalyst; about 0. I 5 parts(030 grams) of solid triethylenediamine catalyst; about 0.033 parts(0.066 grams) of dibutyltindilaurate catalyst. about 5.7 parts (I 1.4grams) of trichlorofluoromethane blowing agent; and about 34.l parts(58.2 grams) of polyisocyanate C3 IOO Index). The cyanoalkyl modifiedsiloxane fluid was used in the form of a siloxane fluid-solvent solutioncomposed of about 10 parts by weight of siloxane fluid and parts byweight of solvent 8] The amount and particular siloxane employed wasvaried and the recorded properties of the various foam samples are givenin TABLE 3 below. assembly and centered so that the propeller shaft wasTABLE 3 Foam Siloxane Siloxane Solution Gurley Foam Cells/ No. Fluid No.Cone. (php) Breathability Inch Shrinkage Cell Uniformity A Control None1.9 12 None Severe Voids Irregular I II 0.3 6.2 22 None Slight VoidsUniform 2 II 0.75 7.5 24 None No Voids Uniform 3 II I.l2 13.2 26 None NoVoids Uniform 4 III 0.3 7.8 24 None No Voids Uniform 5 III 0.75 I 1.2 22None No Voids Uniform 6 III l.l2 I88 28 None No Voids Uniform SiloxanesNot of This Invention 7 XIV (I3 Severe No Voids Uniform 8 XIV 0.75Severe No Voids Uniform 9 XV 0.3 Severe No Voids Uniform I0 XV 0.75Severe No Voids Uniform EXAMPLE 22 about onehalf inch from the bottom ofthe mixer and Another series of high resilience polyether urethane foamwas produced in molded form by employing 100 parts by weight of apolyether blend on the order of about 60 parts (360 grams) of polyethertriol E2 and about 40 parts (240 grams) of polyether triol E3; about 24ccs. of an aqueous premix of about 2.6 parts of water, about 0.] part ofAI catalyst, about l.2 parts of N- ethylmorpholine catalyst and about 0.I2 parts of solid triethylenediamine catalyst, along with about 0.3parts I .8 cc.) ofdibutyltindilaurate catalyst as a five percentsolution in S1. and about 34.7 parts (208.2 grams) of polyisocyanate C3.The amount and particular siloxane fluid used was varied as shown by thefollowing table. The procedure followed consisted of weighing out thepolyol blend and aqueous amine catalyst premix, heating the preparedmold-release coated aluminum mold to a temperature of about 250F.. thenadding the polyol blend and aqueous amine catalyst premix to a 1 /2gallon mixing container followed by the required amount of siloxanefluid and dibutyltindilaurate catalyst. The mixing container was placedon a squat baffle the timer set for 12 minutes. The mixture was agitatedfor 1 minute at 4,000 rpm and allowed to dcgassify (about 25 seconds).Just before the end of degassifcation the required amount ofpolyisocyanate was added and the mixing continued for 5 seconds. Uponcompletion of the mixing the foam forming mixture was rapidly pouredinto the mold which had been cooled or heated to about 5F. above theambient pouring temperature of the mixture. A vented aluminum cover wasclamped on to the mold and the mixture was allowed to foam. rise and geland then the clamped mold was then placed in a hot air oven for about 8and one-half minutes at 300F. before it was removed and demolded. Therecorded properties of the foams so produced are set forth in TABLE 4below. Siloxane VI was used in the form of a Siloxane fluidsolventsolution composed of about 27 parts by weight of siloxane fluid and 73parts by weight of solvent SI. while Siloxane VII, Siloxane XVI andSiloxane XVII were each used as a solution composed of about 22 parts byweight of siloxane fluid and 78 parts by weight of solvent S I.

TABLE 4 Foam Siloxane Siloxane Solution (iurley Foam (ell No. Fluid No.Cone. (php) Breathability Shrinkage Uniformity A None None Sucre VoidsIrregular I VI 0.25 None Slight Voids Irregular 2 VI 0.5 13.4 None NoVoids Uniform 3 VI 0.75 ITS None No Voids Uniform 4 VI I6 207 None NoVoids 7 Uniform 5 VI 2.25 22.7 None No Voids Uniform 6 VI 25 Slight NoVoids Uniform 7 VII 0.25 None Slight Voids Irregular 8 VII 0.5 I7.l NoneNo Voids Uniform 9 VII 0.75 I99 None No Voids Uniform I0 VII L5 204 NoneNo Voids Uniform I I VII 2.25 24.7 NUIIL No Voids Uniform I2 VII 2.5Slight No Voids Uniform I3 XVI 0.25 None Slight Voids Irregular l4 XVI0.5 I28 None No Voids Uniform l5 XVI 0.75 14.2 None No Voids Uniform I6XVI L0 16.] None No Voids Uniform I7 XVI L5 224 None No Voids Uniform I8XVI 2.0 25.2 None No Voids Uniform l9 XVI 2.25 Slight No Voids Uniform20 XVII 0.075 None Slight Voids Irregular 21 XVII 0. I25 I .1 None NoVoids Uniform 22 XVII 0.25 I I.5 None No Voids Uniform 23 XVII 0.5 I2.5None No Voids Uniform 24 XVII 0.75 l5.l None No Voids Uniform 25 XVIIL00 18.3 None No Voids Uniform 26 XVII I.5 22.I None No Voids Uniform 27XVII 1.75 27.] Slight N0 Voids Uniform EXAMPLE 23 Employing a foamformulation similar to that used in Example 20 a series of highresilience polyether urethane foam was produced in a similar mannerusing as The above data in Examples 20-24 demonstrates that theirregular cell structure and voids of the control foams can beeliminated by employing the siloxane fluid stabilizers of this inventionwithout causing any the cyanoalkyl-modified siloxane fluid, SiloxaneXVlll. f Shrmkage l sfloxan fl i not of l mven' Foam NOS We: based on ulaboruory scalemp of tion were found either to not eliminate the voidsof the ingredients while Foam Nm (Fm were based on a control foam or tocause foam shrinkage and therefore Chine scalelup of ingredients Thecyanoukyl modified are not useful as stabilizers in the production ofhigh siloxane fluid (Siloxane XVlll) was used in the form of mslhenc?polyether urethane foam In Cases Slight a siloxane fluid-solventsolution composed of about 25 m a Shrmkuge the non-,nauy regular Crownls p y weight of siloxune fluid 57 parts y weight of slightly puckeredand wrinkled while in cases of moderate foam shrinkage it issubstantially puckered and solvent SI and 18 parts by weight of abutanol started i wrinkled. This surface shrinkage is related to anabnorpoly (oxyethylene-oxypropylene)monool diluent havmal quantity ofclosed cells and tight foam which in ing an average molecular weight ofabout 260 (about 50,7! y wt of the oxyalkylene g p of the diluem turnadversely affects the foams properties such as its being y Oxide units)The amount of Siloxune resiliency, compression set and load hearing Incases fluid employed was varied and the recorded properties of SevereShrmkage the above defects and dlsadvan' of the various foam Samples aregiven in TABLE 5 tages are even more aggravated and pronounced. ln adlowdition severe shrinkage is further evidenced by a pull- TABLE 5 FoamSiloxane Solution Foam Cells/ Cell No. Cone. (php) Breathuhility InchShrinkage Uniformity l 0.3 R2 24 None No Voids 2 0.7 l: 32 None No Voids3 l1] [6.8 32 None No Voids 4 l.5 22.9 34 None No Voids 5 2.1) 27.1 34Slight No Voids 6 0.5 None No Voids 7 0.75 None No Voids l' N t N V 4 9L -33: Nil V313; ll) 1.5 Slight No Voids 7 I bXAMPLE ing away oi thefoam from the sides and/or bottom of Employing a foam formulationsimilar to that used in the mold Thus it is obvious that reasonableamounts of Example 21) a series of high resilience polyether urethesiloxane fluids of this invention can be employed in thane foam wasproduced in a similar manner using a the production of high resiliencepolyether urethane 50:50 7( by weight blend of Siloxane XVI" andSilosfoam whereas such is not the case with the siloxane fluane XIX FoamNos. l-S were based on a laboratory ids not of this invention. scale-upof ingredients while Foam Nos. (F8 were Various modifications andvariations of this inven based on a machine scale-up of ingredients. Theblend tion will be obvious to a worker skilled in the art and ofeyanoalkyl modified siloxane fluids (50 parts by it is to be understoodthat such modifications and variawcight of Siloxane XVlll and 50 partsby weight of Si- 45 tions are to be included within the purview of thisappliloxane XIX} was used in the form of a siloxane fluid cation and thespirit and scope of the appended claims. blend-solvent solution composedof about parts by What is claimed is. weight of the siloxane fluid blendand 70 parts by l. A process for producing high resilience polyetherweight of solvent St. The amount of siloxane fluid u ethane foam. saidprocess comprising foaming and 5t] blend employed was varied and therecorded properties of the various foam samples are given in TABLE 6 below.

TABLE 6 reacting a mixture comprising.

1. organic polyol selected from the group consisting of A) a polyethertriol containing at least mole Siloxznie Solution Foam per cent primaryhydroxyl groups and having a molecular weight from about 2,000 to about8,000 and (B) a mixture of said polyether triol and another polyetherhaving an average of at least two hydroxyl groups, said polyether triolof said mixture amounting to at least 40 weight per cent of the totalpolyol content;

ll. organic polyisocyanate, said organic polyol and said polyisocyanatebeing present in the mixture in a major amount and in the relativeamount required to produce the urethane;

lll. blowing agent in a minor amount sufficient to foam the reactionmixture;

IV. a catalytic amount of catalyst for the production of the urethane;and

V. a cyanoalkyl modified siloxane fluid having the average formulawherein x has a value of l to 6 inclusive; y has a value of to 6inclusive; z has a value of 0 to l inclusive; R is a lower alkyl orphenyl radical; and X is a cyanoalkyl radical of the formula (O),.R'CNwhere n has a value of0 or 1 and R is an alkylene radical having from 2to 4 carbon atoms; said siloxane fluid containing at least one of saidcyanoalkyl radicals and having an average molecular weight in the rangeof about 400 to about 1,500 in an amount sufficient to stabilize thefoam against voids and shrinkage.

2. A process as defined in claim 1 wherein the catalyst is an aminecatalyst, or a mixture of an organic metal catalyst and an aminecatalyst.

3. A process as defined in claim 1 wherein the blowing agent is selectedfrom the group consisting of water, a fluorocarbon compound, andmixtures thereof.

4. A process as defined in claim 1 wherein the polyisocyanate isselected from the group consisting of tol ylene diisocyanate,polymethylene polyphenyl polymeric isocyanates, and mixtures thereof.

5. A process as defined in claim 1 wherein a minor amount of anadditional ingredient selected from the group consisting of a flameretardant agent, an organic solvent for the amine catalyst, an organicsolvent for the cyanoalkyl modified siloxane fluid, and mixtures thereofare also present in the reaction mixture.

6. A process as defined in claim 1 wherein the cyano alky] modifiedsiloxane fluid is employed in the form of a siloxane fluid-organicsolvent solution.

7. A process as defined in claim 1 wherein the organic solvent for thesiloxane fluid is an organic polyether selected from the groupconsisting of mono-ol, diol and triol hydroxy compounds, and mixturesthereof.

8. A process as defined in claim 7 wherein the organic solvent ispolyether triol.

9. A process as defined in claim 6 wherein a catalyst is present as anadditional ingredient in the siloxane fluid-organic solvent solution.

10. A process as defined in claim I wherein the organic polyol polyethertriol contains from about 60 to 90 mole per cent primary hydroxyl groupsand has a molecular weight from about 4,000 to 7,000.

11. A process as defined in claim 10 wherein the organic polyol is amixture of said polyether triol and another polyether having an averageof at least two hydroxyl groups said polyether triol of said mixtureamounting to at least 40 weight per cent of the total polyol content.

12. A process as defined in claim 10 wherein the other polyether is agraft acrylonitrile/polyether triol.

13. A process as defined in claim 10 wherein the cyanoalkyl modifiedsiloxane fluid has an average molecular weight of about 400 to 900;wherein R is a lower alkyl radical, X has a value of 2 to 4 inclusive, yhas a value of l to 4 inclusive, n is 0 and r, is 0.

14. A process as defined in claim 13 wherein R is methyl.

15. A process as defined in claim 14 wherein X is a gamma-cyanopropylradical.

16. A process as defined in claim 10 wherein the cya noalkyl modifiedsiloxane fluid has an average molecular weight of about 400 to 900;wherein R is a lower alkyl radical, x has a value of 2 to 4 inclusive, yhas a value of 0 to 4 inclusive, n is 0 and z is l.

17. A process as defined in claim 16 wherein R is a methyl radical.

18. A process for producing high resilience polyether urethane foam,said process comprising foaming and reacting a mixture comprising:

I. an organic polyol mixture of a polyether triol. said triol containing60 to mole per cent primary hydroxyl groups and having a molecularweight from about 4,000 to 7,000 and another polyether having an averageof at least two hydroxyl groups, said polyether triol of said mixtureamounting to at least 40 weight per cent of the total polyol content;

I]. a polyisocyanate selected from the group consist ing of tolylenediisocyanate, polymethylene polyphenyl polymeric isocyanate, andmixtures thereof, said isocyanates being present in an amount from 90 to10571 of the amount required to provide the stoichiometric amount ofisocyunate groups required to react with the hydroxyl groups of theorganic polyol mixture and any water present as a blowing agent;

Ill. from 2 to 20 parts by weight per I00 parts by weight of the organicpolyol mixture starting material of at least one blowing agent selectedfrom the group consisting of water and fluorocarbon blowing agents;

IV. a catalytic amount of an amine catalyst or a mixture of an organicmetal catalyst and an amine can alyst; and

V. about 0.08 to about 0.6 parts by weight per parts by weight of theorganic polyol mixture starting material of a cyanoalkyl modifiedsiloxane fluid as defined in claim l3.

19. A process as defined in claim 18 wherein R is a methyl radical.

20. A process as defined in claim 19 wherein X is a gamma-cyanopropylradical.

21. A process as defined in claim 18 wherein the cya noalkyl modifiedsiloxane fluid has the average formula wherein Me is a methyl radical.

22. A process as defined in claim 18 wherein the cyanoalkyl modifiedsiloxane fluid has the average formula l cn cu cu civ wherein Me is amethyl radical.

23. A process as defined in claim 18 wherein the cyanoalkyl modifiedsiloxane fluid has the average formula wherein Me is a methyl radical.

24. A process as defined in claim 18 wherein the cyanoalkyl modifiedsiloxane fluid is a blend of 50 parts by weight of a siloxane fluidhaving the average formula (H CH CH CN wherein Me is a methyl radicaland 50 parts by weight of a siloxane fluid having the average formula cucngcn crv wherein Me is a methyl radical.

25. A process as defined in claim 18 wherein the cyanoalkyl modifiedsiloxane fluid is used in the form of a siloxane fluid-organic solventin solution.

26. A process as defined in claim 25 wherein the organic solvent for thesiloxane fluid is an organic polycther selected from the groupconsisting of mono-0|, diol and triol hydroxy compounds, and mixturesthereof.

27. A process as defined in claim 26 wherein the organic solvent ispolyether triol.

28. A process as defined in claim 25 wherein a catalyst is present as anadditional ingredient in the siloxane fluid-organic solvent solution.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION patent 3905924ieptember 16, 1975 lnventoflshm Bela Prokai It is certified that errorappears in the above-identified patent and that said Letters Patent arehereby corrected as shown below:

Column 1, line 48 "foams" should be -foam- Column 5 line 31 "othere"should be other--.

Column 6, line 19, "trimethylolthane" should be -trimethylolethane-.

Column 8, line 52 "[2 ,2 ,l] should be --[2.2 .l]

Column 10, line 59, "suiable" should be ---suitable-.

Column 12 line 18 "fol-" should be --al- Column 13 line 32"cyanoalkylmodi" should be -cyanoalkyl-modi- Column 14, line 51"refered" should be --referred.

Column 17 line 36 "noalkylmodified" should be ---noalkylmodified--.

Column 22, line 34 "fluidsolvent" should be --fluid solvent-.

Column 23, the heading of the first column in TABLE 6 shown as "0am"should be -Foam---.

Column 28, line 10 (claim 25 line 3) the term "in" should be deleted.

Signed and Scaled this twentieth D f January 1976 I [SEAL] Attest:

RUTH C. MASON C. MARSHALL DANN Arresting Office Commissioner ojParentsand Trademarks

1. A PROCESS FOR PRODUCING HIGH RESILIENCE POLYETHER URETHANE FOAM, SAIDPROCESS COMPRISING FOAMING AND REACTING A MIXTURE COMPRISING: I. ORGANICPOLYOL SELECTED FROM THE GROUP CONSISTING OF (A) A POLYETHER TRIOLCONTAINING AT LEAST 40 MOL PER CENT PRIMARY HYDROXYL GROUPS AND HAVING AMOLECULAR WEIGHT FROM ABOUT 2,000 TO ABOUT 8,000 AND (B) A MIXTURE OFSAID POLYETHER TRIOL AND ANOTHER POLYETHER HAVING AN AVERAGE OF AT LEASTTWO HYDROXYL GROUPS, SAID POLYETHER TRIOL OF SAID MIXTURE AMOUNTING TOAT LEAST 40 WEIGHT PER CENT OF THE TOTAL POLYOL CONTENT, II. ORGANICPOLYISOCYANATE, SAID ORGANIC POLYOL AND SAID POLYISOCYANATE BEINGPRESENT IN THE MIXTURE IN A MAJOR AMOUNT AND IN THE RELATIVE AMOUNTREQUIRED TO PRODUCE THE URETHANE, III. BLOWING AGENT IN A MINOR AMOUNTSUFFICIENT TO FOAM THE REACTION MIXTURE, IV. A CATALYTIC AMOUNT OFCATALYST FOR THE PRODUCTION OF THE URETHANE, AND V. A CYANOALKY MODIFIEDSILOXANE FLUID HAVING THE AVERAGE FORMULA
 2. A process as defined inclaim 1 wherein the catalyst is an amine catalyst, or a mixture of anorganic metal catalyst and an amine catalyst.
 3. A process as defined inclaim 1 wherein the blowing agent is selected from the group consistingof water, a fluorocarbon compound, and mixtures thereof.
 4. A process asdefined in claim 1 wherein the polyisocyanate is selected from the groupconsisting of tolylene diisocyanate, polymethylene polyphenyl polymericisocyanates, and mixtures thereof.
 5. A process as defined in claim 1wherein a minor amount of an additional ingredient selected from thegroup consisting of a flame retardant agent, an organic solvent for theamine catalyst, an organic solvent for the cyanoalkyl modified siloxanefluid, and mixtures thereof are also present in the reaction mixture. 6.A process as defined in claim 1 wherein the cyanoalkyl modified siloxanefluid is employed in the form of a siloxane fluid-organic solventsolution.
 7. A process as defined in claim 1 wherein the organic solventfor the siloxane fluid is an organic polyether selected from the groupconsisting of mono-ol, diol and triol hydroxy compounds, and mixturesthereof.
 8. A process as defined in claim 7 wherein the organic solventis polyether triol.
 9. A process as defined in claim 6 wherein acatalyst is present as an additional ingredient in the siloxanefluid-organic solvent solution.
 10. A process as defined in claim 1wherein the organic polyol polyether triol contains from about 60 to 90mole per cent primary hydroxyl groups and has a molecular weight fromabout 4, 000 to 7,000.
 11. A process as defined in claim 10 wherein theorganic polyol is a mixture of said polyether triol and anotherpolyether having an average of at least two hydroxyl groups saidpolyether triol of said mixture amounting to at least 40 weight per centof the total polyol content.
 12. A process as defined in claim 10wherein the other polyether is a graft acrylonitrile/polyether triol.13. A process as defined in claim 10 wherein the cyanoalkyl modifiedsiloxane fluid has an average molecular weight of about 400 to 900;wherein R is a lower alkyl radical, X has a value of 2 to 4 inclusive, yhas a value of 1 to 4 inclusive, n is 0 and z is
 0. 14. A process asdefined in claim 13 wherein R is methyl.
 15. A process as defined inclaim 14 wherein X is a gamma-cyanopropyl radical.
 16. A process asdefined in claim 10 wherein the cyanoalkyl modified siloxane fluid hasan average molecular wEight of about 400 to 900; wherein R is a loweralkyl radical, x has a value of 2 to 4 inclusive, y has a value of 0 to4 inclusive, n is 0 and z is
 1. 17. A process as defined in claim 16wherein R is a methyl radical.
 18. A process for producing highresilience polyether urethane foam, said process comprising foaming andreacting a mixture comprising: I. an organic polyol mixture of apolyether triol, said triol containing 60 to 90 mole per cent primaryhydroxyl groups and having a molecular weight from about 4,000 to 7,000and another polyether having an average of at least two hydroxyl groups,said polyether triol of said mixture amounting to at least 40 weight percent of the total polyol content; II. a polyisocyanate selected from thegroup consisting of tolylene diisocyanate, polymethylene polyphenylpolymeric isocyanate, and mixtures thereof, said isocyanates beingpresent in an amount from 90 to 105% of the amount required to providethe stoichiometric amount of isocyanate groups required to react withthe hydroxyl groups of the organic polyol mixture and any water presentas a blowing agent; III. from 2 to 20 parts by weight per 100 parts byweight of the organic polyol mixture starting material of at least oneblowing agent selected from the group consisting of water andfluorocarbon blowing agents; IV. a catalytic amount of an amine catalystor a mixture of an organic metal catalyst and an amine catalyst; and V.about 0.08 to about 0.6 parts by weight per 100 parts by weight of theorganic polyol mixture starting material of a cyanoalkyl modifiedsiloxane fluid as defined in claim
 13. 19. A process as defined in claim18 wherein R is a methyl radical.
 20. A process as defined in claim 19wherein X is a gamma-cyanopropyl radical.
 21. A process as defined inclaim 18 wherein the cyanoalkyl modified siloxane fluid has the averageformula
 22. A process as defined in claim 18 wherein the cyanoalkylmodified siloxane fluid has the average formula
 23. A process as definedin claim 18 wherein the cyanoalkyl modified siloxane fluid has theaverage formula
 24. A process as defined in claim 18 wherein thecyanoalkyl modified siloxane fluid is a blend of 50 parts by weight of asiloxane fluid having the average formula
 25. A process as defined inclaim 18 wherein the cyanoalkyl modified siloxane fluid is used in theform of a siloxane fluid-organic solvent in solution.
 26. A process asdefined in claim 25 wherein the organic solvent for the siloxane fluidis an organic polyether selected from the group consisting of mono-ol,diol and triol hydroxy compounds, and mixtures thereof.
 27. A process asdefined in claim 26 wherein the organic solvent is polyether triol. 28.A process as defined in claim 25 wherein a catalyst is present as anadditional ingredient in the siloxane fluid-organic solvent solution.